CN1227334C - Superfine granular zeolite aromatizing catalyst and its preparation and use - Google Patents
Superfine granular zeolite aromatizing catalyst and its preparation and use Download PDFInfo
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Abstract
The present invention discloses an ultrafine particle zeolite aromatization catalyst, a preparation method thereof and an application thereof in a hydrorefining/aromatization combined technology of complete fractional FCC gasoline. The catalyst comprises the following composition by using the catalyst weight as the reference: 1.0 wt% to 10.0 wt% of total content of transition metal oxides and lanthanide series rare earth metal oxides, 50.0 wt% to 90.0 wt% of ultrafine particle zeolite, and a surplus quantity of inorganic oxide adhesive agent. The crystal particle size of the ultrafine particle zeolite is from 20 nm to 800 nm. Due to the low total acid quantity of the ultrafine particle zeolite aromatization catalyst, particularly a low L acid quantity and smooth pore canals, the catalyst has the advantages of high coking resisting capability and high stability, and in addition, few anti-knock index ((R+M)/2) losses of an obtained gasoline product are guaranteed while the sulfur content and the olefine content of the FCC gasoline can be reduced.
Description
1, technical field
The present invention relates to a kind of ultrafine particle zeolite aromatized catalyst and preparation method thereof and the application in catalytic gasoline of whole fraction hydrogenating desulfurization and aromizing combination process.
2, background technology
Along with the rapid raising of people's environmental consciousness, the atmospheric pollution that vehicle exhaust causes is paid close attention to by people day by day.The alkene and the sulphur content that reduce in the gasoline can reduce volatile organic compounds in the vehicle exhaust (VOCs), oxynitride (NO
X), emission of harmful substances such as sulfurous gas.What for this reason, oneself had all been formulated in countries in the world turns to the clean gasoline new standard of sign with low-sulfur and low alkene.The sulphur content of the EU2005 of European Union standard code European clean gasoline after 2005 is not more than 50 μ g/g, and olefin(e) centent is 14v%～18v%; The sulphur content of U.S. U.S.EPATier2 standard code U.S.'s clean gasoline after 2006 is not more than 80 μ g/g, and olefin(e) centent is not more than 14v%; The clean gasoline new standard GB17930-1999 that China formulates requires the sulphur content of motor spirit to be not more than 800 μ g/g, and olefin(e) centent is not more than 35.0v%.This standard will be carried out in the whole nation on January 1st, 2003.Main production and selling merchant as China's gasoline, Sinopec Group has formulated stricter company standard Q/SHR007-2000, this standard-required was from January 1st, 2003, the sulphur content of big city gasoline such as supply Beijing, Shanghai and Guangzhou will be reduced to and be not more than 200 μ g/g, olefin(e) centent is not more than 30.0v%, olefin(e) centent adds aromatic hydrocarbons and is not more than 60.0v%, and benzene content is not more than 2.0v%.Along with China's accession to the WTO (WTO), the standard of gasoline can progressively walk with world's pace, and the sulphur content and the olefin(e) centent of following gasoline can be more and more lower.
At present, China's plant catalytic cracking (FCC) sulfur in gasoline content is 200～1500 μ g/g, and olefin(e) centent is 40.0v%～50.0v%, and research octane number (RON) (abbreviating RON as) is 90～94.Catalytically cracked gasoline accounts for the 80wt%～90wt% of oil refinery gasoline harmonic proportion usually.Therefore, the sulphur content of reduction catalytically cracked gasoline and olefin(e) centent are to satisfy the more and more key of strict clean gasoline new spec of China.
Though adopt traditional hydrofining technology can remove sulfide and olefin(e) compound in the catalytically cracked gasoline effectively, but because the higher low-octane alkane of the saturated generation of hydrogenation of olefins of octane value, so, adopt traditional Hydrobon catalyst and technology when desulfurization and reducing olefin(e) centent, must follow the rapid decline of gasoline octane rating.Generally, the desulfurization degree of catalytic gasoline is 90% o'clock, 5.0～8.0 units of anti-knock index ((R+M)/2) loss.Consume a large amount of hydrogen simultaneously.How reducing the saturated loss of octane number that causes of alkene is the difficult point of catalytic gasoline in hydrogenating desulfurization and reduction olefin(e) centent problem.
Because sulphur concentrates on than last running, alkene and concentrates on lighter fraction in the catalytically cracked gasoline.In the former document, propose many schemes and removed sulfide, kept the alkene that octane value is had positive contribution simultaneously.For example, US3,759,821, US4, the method for 062,762 disclosed upgrading catalytically cracked gasoline all is to be 2 kinds or 3 kinds of cuts with the catalytically cracked gasoline fractionation, every kind of cut diverse ways sulphur removal merges these cuts then.US5,362,376 technologies of having introduced a kind of catalyzed gasoline hydrogenation desulfurization and having selected shape hydrocracking two-stage catalytic agent combination.The catalytically cracked gasoline last running that is characterized in prefractionation is after hydrogenating desulfurization, pass through mesopore, tart NiO/HZSM-5 molecular sieve catalyst shape slective cracking again, thereby recover because of the saturated loss of octane number that causes of hydrogenation of olefins in the hydrodesulfurization process, and then be in harmonious proportion with lighting end.Above-mentioned catalytically cracked gasoline prefractionation hydrodesulfurization is all developed at the characteristics of its olefin(e) centent lower (about 20v%), aromatic hydrocarbons higher (about 40v%), the alkene saturation exponent of these technologies has only about 20% usually, and the amplitude that reduces alkene is limited.And in order to satisfy the requirement of China's clean gasoline new standard to olefin(e) centent, catalytic gasoline alkene saturation exponent is wanted about 50% usually.Therefore, above-mentioned technology is relatively poor to the adaptability of raw material, and loss of octane number is more, can not satisfy China to the catalytic gasoline desulfurization, the requirement of alkene is fallen.
CN1350051A discloses the Catalysts and its preparation method that a kind of low-quality gasoline upgrading is produced clean gasoline.Thick pressure gasoline carries out upgrading containing on the little crystal grain HZSM-5 of rare-earth oxide, obtains low alkene, low benzene and doctor negative clean gasoline.Though, adopted the acid little crystal grain HZSM-5 carrier of hydrothermal treatment consists to reduce its strength of acid and sour density in this patent application, this aromatized catalyst coking deactivation is very fast, and catalytic performance stability is not ideal enough.Though this is that the aluminium that takes off from skeleton forms aluminium cations outside the skeleton (EFAl) outside zeolite framework because of the acidic zeolite catalyst after the hydrothermal treatment consists, the silica alumina ratio of product is improved, total acid and B acid amount reduce.But, under the temperature of 550～650 ℃ of normally used hydrothermal treatment consists, can increase because of the zeolite framework dehydroxylation seriously makes L acid amount, the outer aluminium cations (EFAl) of simultaneously a large amount of skeletons retains in the zeolite cavity, can increase the diffusional resistance of reactant molecule in the catalyzer duct, prolongs the product residence time of molecule in catalyzer, aggravation unsaturated hydrocarbon molecule polymeric degree on above-mentioned L acidic site, cause the catalyzer coking, slacken the catalytic activity of catalyzer, reduce the stability of catalyzer.
Catalytically cracked gasoline contains the diolefin of 2.0v%～5.0v% usually except containing the alkene about 45.0v%.At high temperature, diolefin is easy to polymerization on the strongly-acid position on acid molecular sieve catalyst surface, causes the catalyzer coking, slackens the catalytic activity of catalyzer, reduces the stability of catalyzer.Can make when serious between reactor inlet and the outlet and produce bigger pressure difference (abbreviation pressure drop), shorten the on-stream time of device.
3, summary of the invention
The objective of the invention is to propose a kind of L acid and measure low, that the duct is unimpeded ultrafine particle zeolite aromatized catalyst and preparation method thereof and the application in full cut FCC gasoline hydrofinishing/aromizing combination process.This catalyzer anti-coking performance is strong, good stability, and can be in the sulphur content and olefin(e) centent that reduce FCC gasoline, the loss of the anti-knock index ((R+M)/2) of the clean gasoline product that assurance is produced is less.
A kind of ultrafine particle zeolite aromatized catalyst provided by the invention, weight with catalyzer is benchmark, its composition comprises: transition metal oxide and lanthanide rare metal oxide content sum are 1.0wt%～10.0wt%, the ultrafine particle zeolite content is 50.0wt%～90.0wt%, surplus is an inorganic oxide adhesive, and the grain fineness number of ultrafine particle zeolite is 20～800nm; The B acid of ultrafine particle zeolite aromatized catalyst, L acid and total acid content are respectively: 0.020mmol/g～0.080mmol/g, 0.100mmol/g～0.250mmol/g and 0.120mmol/g～0.330mmol/g.The acid amount of catalyzer is measured on the IR instrument among the present invention, is adsorbate with the pyridine, measures 400 ℃ of pyridines in the acid amount of chemisorbed on catalyst amount as catalyzer on recording quartz spring weight absorption instrument.
Above-mentioned transition metal oxide is one or more in zinc oxide, ferric oxide, manganese oxide, nickel oxide, cobalt oxide, molybdenum oxide and the Tungsten oxide 99.999, particularly nickel oxide, molybdenum oxide and zinc oxide, the lanthanide rare metal oxide is lanthanum trioxide and/or cerium oxide, particularly lanthanum trioxide.
The specific surface area of above-mentioned ultrafine particle zeolite catalyst is 300m
2/ g～550m
2/ g, pore volume are 0.15ml/g～0.45ml/g, average pore diameter 1.5nm～3.5nm.
Above-mentioned ultrafine particle zeolite is one or more among HZSM-5, HL, HBeta, HM, HMCM-41, HSAPO-5, HSAPO-11, HSAPO-31 and the HSAPO-41, particularly HZSM-5 and/or HBeta, preferably HZSM-5 and HBeta.
Described tackiness agent is titanium oxide, aluminum oxide, silicon oxide or aluminium oxide-silicon oxide.
The preparation method of ultrafine particle zeolite aromatized catalyst provided by the present invention may further comprise the steps:
A, ultrafine particle zeolite and inorganic oxide adhesive are mixed, after extruded moulding, drying, roasting, prepare ultrafine particle zeolite Aromatizatian catalytic agent carrier intermediate;
After b, said catalyst carrier intermediate carry out hydrothermal treatment consists, adding equivalent concentration in the ratio of liquid/solid volume than 1.5: 1.0～5.0: 1.0 is 0.1～2.0N, be preferably the dilute inorganic acid solution of 0.2～1.0N, after rinsing, drying, roasting, prepare ultrafine particle zeolite Aromatizatian catalytic agent carrier;
C, with above-mentioned carrier incipient impregnation in the aqueous solution that contains transition metal and lanthanide rare metal, then, filter, dry, roasting, prepare the ultrafine particle zeolite aromatized catalyst that contains transition metal oxide and lanthanide rare metal oxide.
Among the above-mentioned preparation method, method of the prior art is all adopted in drying described in step a, b and the c and roasting.
Described drying of above-mentioned steps a and roasting process were to descend dry 8～15 hours at 100 ℃～140 ℃, 400 ℃～600 ℃ following roastings 3～10 hours.
Diluted mineral acid is dilute hydrochloric acid, rare nitric acid, dilute phosphoric acid or rare carbonic acid among the above-mentioned steps b; Described hydrothermal treatment consists process is to adopt method of the prior art, at water/solid volume ratio is to be warming up to 500～600 ℃ under 1: 1～10: 1 the water vapour atmosphere, and thermostat(t)ed water thermal treatment 3～15 hours under this temperature; Described rinsing, drying and roasting process stir down rinsings in temperature being 20～100 ℃, 100 ℃～140 ℃ dry 8～15 hours down, 400 ℃～500 ℃ following roastings 3～10 hours; The water-intake rate of gained support of the catalyst is 0.50ml/g～0.70ml/g.
The aqueous solution that contains transition metal and lanthanide rare metal among the above-mentioned steps c is normally formulated by its nitrate or vitriol or ammonium salt; Described drying and roasting process were to descend dry 8～15 hours at 100 ℃～140 ℃, 400 ℃～500 ℃ following roastings 3～10 hours.
Catalyzer of the present invention can be applied to catalytic gasoline hydrogenating desulfurization, fall in the olefin process.Thereby reach when desulfurization and reducing olefin(e) centent the less purpose of anti-knock index loss of product.This technology specific operation process is:
The first stage catalytic cracking gasoline hydrofinishing: catalytic gasoline of whole fraction is contacted with Hydrobon catalyst under the hydrorefined condition of demulcent, to remove sulfide, the part olefin(e) compound in the gasoline, particularly to remove the diolefin of easy polymerization coking under the high temperature fully.
Second section light-hydrocarbon aromatized recovery octane value: with first section hydrotreated product process ultrafine particle zeolite aromatized catalyst of the present invention, with light-hydrocarbon aromatized be aromatic hydrocarbons, with the anti-knock index loss that recovers to cause because of hydrogenation of olefins in the unifining process is saturated, isomerization of carrying out and cracking reaction simultaneously also played certain booster action to octane value recovering.
Said Hydrobon catalyst can be the Hydrobon catalyst of any routine in first section, preferably Mo-Co or Mo-Ni/ aluminium oxide catalyst.Said demulcent hydrofining condition is: reaction pressure 2.5MPa～4.5MPa, 180 ℃～280 ℃ of temperature of reaction, volume space velocity 2.0h
-1～10.0h
-1With hydrogen to oil volume ratio 200～800: 1.The reaction conditions of second section described aromizing is: reaction pressure 2.5MPa～4.5MPa, 340 ℃～420 ℃ of temperature of reaction, volume space velocity 0.5h
-1～3.0h
-1With hydrogen to oil volume ratio 200～800: 1.
Because first section unifining process is thermopositive reaction, generally can produce 30 ℃～100 ℃ temperature rises along reactor bed, and second section octane value recovering aromatization process is thermo-negative reaction, and need high slightly temperature, therefore, Hydrobon catalyst and the octane value recovering aromatized catalyst filling of preferably connecting.Both can connect and be contained in the same reactor.For the ease of control, preferably be contained in respectively in two reactors.
4, embodiment
The concrete preparation method of ultrafine particle zeolite aromatized catalyst provided by the present invention may further comprise the steps:
A, ultrafine particle zeolite and inorganic oxide adhesive are mixed, grind evenly, adding concentration is the aqueous nitric acid of 3.0～8.0g/100ml, be rolled into extruded moulding after the wet cake of micelle shape, drying is 8～15 hours under 100 ℃～140 ℃, 400 ℃～600 ℃ following roastings 3～10 hours, prepare ultrafine particle zeolite Aromatizatian catalytic agent carrier intermediate;
B, the said catalyst carrier intermediate is packed in the activation furnace, be to be warming up to 500～600 ℃ under the atmosphere of 1: 1～10: 1 water vapors at water/solid volume ratio, and thermostat(t)ed water thermal treatment 3～15 hours under this temperature, then, stop into water steam, swap-in contains the nitrogen oxygen atmosphere that nitrogen content is 85wt%～95wt%, and the wet steam displacement of adsorbing on the catalyzer is clean, after control is cooled to room temperature, draw off; Get the sample of above-mentioned hydrothermal treatment consists and put into beaker, adding equivalent concentration in the ratio of liquid/solid volume than 1.5: 1.0～5.0: 1.0 is the dilute inorganic acid solution of 0.1～2.0N, be 20～100 ℃ in temperature and stir rinsing 2～5 times down, then, 100 ℃～140 ℃ dry down 8～15 hours, 400 ℃～500 ℃ following roastings 3～10 hours, prepare ultrafine particle zeolite Aromatizatian catalytic agent carrier;
C, with above-mentioned carrier incipient impregnation in the aqueous solution that contains transition metal and lanthanide rare metal 5～10 hours, after the filtration, drying is 8～15 hours under 100 ℃～140 ℃, 400 ℃～500 ℃ following roastings 3～10 hours, prepare the ultrafine particle zeolite aromatized catalyst that contains transition metal oxide and lanthanide rare metal oxide.
Embodiment 1
Present embodiment prepares 2.0wt%NiO-0.50wt%ZnO-1.50wt%La
2O
3/ grain fineness number is 90nm～500nmHZSM-5 aromatized catalyst.
Take by weighing 229.6gHZSM-5 (SiO
2/ Al
2O
3Mol ratio is 27), 140.0gAl
2O
3, and their ground and mixed is even, adding 150ml concentration is the dilute nitric acid solution of 5.6g/100ml, grinds to form uniform muffin body.On banded extruder, be extruded into the bar that diameter is 2.0mm.After drying under the room temperature, drying is 12 hours under 100 ℃, 500 ℃ of following roastings 10 hours, makes ultrafine particle HZSM-5 Aromatizatian catalytic agent carrier intermediate.
100ml said catalyst carrier intermediate is packed in the vertical activation furnace, is to be warming up to 510 ℃ under the water vapour atmosphere of 150ml/h at water-flowing amount, and thermostat(t)ed water thermal treatment 12 hours under this temperature.Then, stop into water steam, swap-in contains the nitrogen oxygen atmosphere of nitrogen 90wt%, and the wet steam displacement of adsorbing on the catalyzer is clean, after control is cooled to room temperature, draws off.
Get the sample of the above-mentioned hydrothermal treatment consists of 60g again and put into beaker, adding equivalent concentration in the ratio of liquid/solid volume than 1.5: 1 is the dilute hydrochloric acid solution of 0.30N, is 40 ℃ of slight down stirring rinsings 4 times in temperature.Then, 100 ℃ of dry down 11 hours, 490 ℃ following roastings 6 hours.Take out after reducing to room temperature, prepare ultrafine particle HZSM-5 zeolite Aromatizatian catalytic agent carrier.
Take by weighing said catalyst carrier 50g and put into and spray jar, start rotor pump.In 30 minutes, 35ml contained 1.0gNiO, 0.25gZnO and 0.75gLa
2O
3Nickelous nitrate, zinc nitrate and lanthanum nitrate hexahydrate spray in the support of the catalyst.After drying under the room temperature, 100 ℃ dry 13 hours down, 490 ℃ of following roastings 6 hours, make the ultrafine particle HZSM-5 aromatized catalyst of nickeliferous, zinc and lanthanum, be numbered UZ.This catalyzer rerum natura is listed in the table 1.
Embodiment 2
Present embodiment prepares 4.0wt%MoO
3-1.0wt%ZnO-3.0wt%La
2O
3/ grain fineness number is 70nm～50nmHBeta aromatized catalyst.
Take by weighing 239.6gHBeta (SiO
2/ Al
2O
3Mol ratio is 33), 140.0gAl
2O
3, and their ground and mixed is even, adding 180ml concentration is the dilute nitric acid solution of 3.6g/100ml, grinds to form uniform muffin body.On banded extruder, be extruded into the bar that diameter is 2.0mm.After drying under the room temperature, drying is 10 hours under 120 ℃, 510 ℃ of following roastings 8 hours, makes ultrafine particle HBeta zeolite Aromatizatian catalytic agent carrier intermediate.
100ml said catalyst carrier intermediate is packed in the vertical activation furnace, is to be warming up to 520 ℃ under the atmosphere of 300ml/h water vapor at water-flowing amount, and thermostat(t)ed water thermal treatment 10 hours under this temperature.Then, stop into water steam, swap-in contains the nitrogen oxygen atmosphere of nitrogen 85wt%, and the wet steam displacement of adsorbing on the catalyzer is clean, after control is cooled to room temperature, draws off.
Get the sample of the above-mentioned hydrothermal treatment consists of 60g again and put into beaker, adding equivalent concentration in the ratio of liquid/solid volume than 2.5: 1 is the dilute nitric acid solution of 1.0N, is 80 ℃ of slight down stirring rinsings 2 times in temperature.Then, 120 ℃ of dry down 9 hours, 480 ℃ following roastings 8 hours.Take out after reducing to room temperature, prepare ultrafine particle HBeta zeolite Aromatizatian catalytic agent carrier.
Take by weighing said catalyst carrier 50g and put into and spray jar, start rotor pump.In 30 minutes, 45ml is contained 2.0gMoO
3, 0.50gZnO and 1.5gLa
2O
3The aqueous solution of ammonium molybdate, zinc nitrate and lanthanum nitrate spray in the support of the catalyst.After drying under the room temperature, drying is 10 hours under 110 ℃, 480 ℃ of following roastings 8 hours, makes the ultrafine particle HBeta zeolite aromatized catalyst that contains molybdenum, zinc and lanthanum, is numbered UB.This catalyzer rerum natura is listed in the table 1.
Embodiment 3
Present embodiment prepares 3.0wt%NiO-0.8wt%ZnO-4.0wt%La
2O
3(the HBeta/HZSM-5 weight percent is/HBeta+HZSM-5: aromatized catalyst 50%/50%).Wherein the HBeta grain fineness number is 70nm～150nm; The HZSM-5 grain fineness number is 90nm～500nm.
Take by weighing 118.8g HBeta (SiO
2/ Al
2O
3Mol ratio is 33), 106.0g HZSM-5 (SiO
2/ Al
2O
3Mol ratio is 27), 140.0gAl
2O
3, and their ground and mixed is even, adding 170ml concentration is the dilute nitric acid solution of 7.6g/100ml, grinds to form uniform muffin body.On banded extruder, be extruded into the bar that diameter is 2.0mm.After drying under the room temperature, drying is 9 hours under 130 ℃, 520 ℃ of following roastings 6 hours, makes ultrafine particle HBeta+HZSM-5 zeolite Aromatizatian catalytic agent carrier intermediate.
100ml said catalyst carrier intermediate is packed in the vertical activation furnace, is to be warming up to 550 ℃ under the atmosphere of water vapor of 500ml/h at water-flowing amount, and thermostat(t)ed water thermal treatment 6 hours under this temperature.Then, stop into water steam, swap-in contains the nitrogen oxygen atmosphere of nitrogen 90wt%, and the wet steam displacement of adsorbing on the catalyzer is clean, after control is cooled to room temperature, draws off.
Get the sample of the above-mentioned hydrothermal treatment consists of 60g again and put into beaker, adding equivalent concentration in the ratio of liquid/solid volume than 4: 1 is the dilute phosphoric acid solution of 1.8N, is 60 ℃ of slight down stirring rinsings 3 times in temperature.Then, 130 ℃ of dry down 8 hours, 470 ℃ following roastings 10 hours.Take out after reducing to room temperature, prepare ultrafine particle HBeta+HZSM-5 zeolite Aromatizatian catalytic agent carrier.
Take by weighing said catalyst carrier 50g and put into and spray jar, start rotor pump.In 30 minutes, 40ml contained 1.5gNiO, 0.40gZnO and 2.0gLa
2O
3Nickelous nitrate, zinc nitrate and lanthanum nitrate hexahydrate spray in the support of the catalyst.After drying under the room temperature, 130 ℃ dry 9 hours down, 470 ℃ of following roastings 10 hours, make the ultrafine particle HBeta+HZSM-5 zeolite aromatized catalyst of nickeliferous, zinc and lanthanum, be numbered UBZ.This catalyzer rerum natura is listed in the table 1.
Comparative example 1
This comparative example prepares the zeolite aromatized catalyst according to the composition of embodiment 1.But the carrier after the hydrothermal treatment consists is without the diluted mineral acid cleanup acid treatment, and other step and embodiment 1 are in full accord.This comparison catalyzer is numbered UZ-C.This catalyzer rerum natura is listed in the table 1.
Comparative example 2
This comparative example prepares the zeolite aromatized catalyst according to the composition of embodiment 3.But the carrier after the hydrothermal treatment consists is without the diluted mineral acid cleanup acid treatment, and other step and embodiment 3 are in full accord.This comparison catalyzer is numbered UBZ-C.This catalyzer rerum natura is listed in the table 1.
The rerum natura of table 1 zeolite aromatized catalyst
| Project | Embodiment 1 | Comparative example 1 | Embodiment 2 | Embodiment 3 | Comparative example 2 | |
| The catalyzer numbering | UZ | UZ-C | UB | UBZ | UBZ-C | |
| NiO，wt％ | 2.0 | 2.0 | - | 3.0 | 3.0 | |
| MoO 3，wt％ | - | - | 4.0 | - | - | |
| ZnO，wt％ | 0.5 | 0.5 | 1.0 | 0.8 | 0.8 | |
| La 2O 3，wt％ | 1.5 | 1.5 | 3.0 | 4.0 | 4.0 | |
| Specific surface area, m 2/g | 330 | 305 | 480 | 390 | 360 | |
| Pore volume, ml/g | 0.25 | 0.22 | 0.40 | 0.35 | 0.33 | |
| Average pore diameter, nm | 1.90 | 1.82 | 3.50 | 3.11 | 2.82 | |
| Acid *Character | B acid | 0.031 | 0.038 | 0.047 | 0.042 | 0.045 |
| L acid | 0.126 | 0.167 | 0.175 | 0.164 | 0.194 | |
| Total acid content | 0.157 | 0.205 | 0.222 | 0.206 | 0.239 | |
*Acid matter is measured on the IR instrument, is adsorbate with the pyridine, measures 400 ℃ of pyridines in the acid amount of chemisorbed on catalyst amount as catalyzer, unit: mmol/g on recording quartz spring weight absorption instrument.
Embodiment 5
The catalytic performance of the more above-mentioned aromatized catalyst of present embodiment and anti-carbon deposit performance.
Test is to carry out on the device of two reactors in series, and each reactor can be adorned the 100ml catalyzer.A kind of commodity Hydrobon catalyst FH-98:WO packs in first reactor
3(20.0wt%)-MoO
3(9.0wt%)-NiO (4.5wt%)/Al
2O
320ml dilutes with porcelain is husky with 2: 1 ratios; The above-mentioned aromatized catalyst 40ml that packs in second reactor, with 2: 1 ratios with the husky dilution of porcelain.Airtight qualified after, at first carry out presulfiding of catalyst.Vulcanized oil is a straight-run spirit, and vulcanizing agent is CS
2, CS
2Concentration is 1.0v%; Sulfide stress is 2.0MPa, temperature be 230 ℃ following 8 hours, 280 ℃ are following 8 hours; The vulcanized oil volume space velocity is 2.0h
-1Sulfuration is brought up to 3.2MPa with reaction pressure after finishing.Swap-in catalytic gasoline raw material then, an anti-volume space velocity is 4.0h
-1, two anti-volume space velocities are 2.0h
-1In 3 hours, one instead is cooled to 220 ℃, and two instead are warming up to 400 ℃.After stablizing 48 hours, sampling analysis.Be controlled at each runtime into behind the catalytic gasoline raw material 500 hours, and stopped work then, draw off catalyzer, measure catalyzer coke content.
Table 2 has been listed the used catalytic gasoline raw material of evaluation test oil properties; Table 3 has been listed the result of above-mentioned test.
Table 2 catalytically cracked gasoline raw material oil properties
| Project | Catalytically cracked gasoline |
| Density, g/ml | 0.7250 |
| Sulphur content, μ g/g | 300 |
| Olefin(e) centent, v% | 46.8 |
| Aromaticity content, v% | 16.0 |
| Research octane number (RON), RON | 93.0 |
| Anti-knock index, (R+M)/2 | 85.0 |
| Boiling range, ℃ | |
| IBP/10％ | 39.6/57.9 |
| 30％/50％ | 71.5/92.2 |
| 70％/90％ | 121.2/155.5 |
| 95％/EBP | 161.1/184.5 |
Table 3 catalytically cracked gasoline desulfurization/the fall character of olefin product
| Catalyzer | Sulphur content | Olefin(e) centent | Aromaticity content | (R+M)/2 loss | Liquid yield | Carbon deposit |
| μg/g | v％ | v％ | wt％ | wt％ | ||
| Catalyzer UZ | 47 | 18.2 | 28.6 | 0.7 | 92 | 7.5 |
| Catalyzer UZ-C | 48 | 19.9 | 27.2 | 0.8 | 88 | 9.8 |
| Catalyzer UB | 45 | 20.3 | 26.5 | 1.0 | 85 | 4.6 |
| Catalyzer UBZ | 43 | 18.7 | 27.0 | 0.9 | 90 | 5.0 |
| Catalyzer UBZ-C | 49 | 21.6 | 23.5 | 1.5 | 86 | 7.2 |
As can be seen, the ultrafine particle HZSM-5 catalyzer UZ that carries out cleanup acid treatment after the hydrothermal treatment consists again compares with independent hydrothermal treatment consists HZSM-5 catalyzer UZ-C in the table 3, and the former aromizing selectivity is apparently higher than the latter, and loss of octane number is lower, and yield of gasoline is higher.In same runtime, the former has reduced 24% by coke content approximately.This is because pickling-rinsing has fallen the non-framework aluminum positively charged ion (EFAl) in the zeolite cavity, catalyst surface area has improved nearly 10%, pore volume has improved nearly 15%, average pore diameter has increased nearly 6%, therefore, the duct is more unimpeded, and reactant molecule has strengthened the selectivity of FCC aromatization of gas easily near catalyst active center; Pickling has simultaneously also reduced the acid sites number, L acid site particularly, thus suppressed the degree of scission reaction, improved the yield of gasoline product liquid, also, reduced coke content, improved the stability of catalyzer in the degree that has to a certain degree reduced secondary side reactions such as polymerization coking.Compound ultrafine particle HZSM-5+HBeta catalyzer also shows same effect.
From table 3 more as can be seen, ultrafine particle HZSM-5 catalyzer UZ compares with ultrafine particle HBeta catalyzer UB, under the close situation of desulfurization degree, the former aromizing selectivity is higher, loss of octane number is lower, and yield of gasoline is higher, shows that it is a kind of good FCC aromatization of gas catalyzer, but greater catalytic agent coke content is indicating that the permanent stability of catalyzer are relatively poor.As can be seen from Table 1, ultrafine particle HZSM-5 zeolite catalyst pore volume, average pore diameter are less, thereby have increased the residence time of reactant molecule in catalyst pores, have deepened the degree of depth that aromatization carries out.Also increase simultaneously the degree of secondary side reactions such as hydrogen transference, polymerization coking, caused the coke content on the catalyzer to increase.In addition, the acidity of ultrafine particle HZSM-5 zeolite catalyst UZ than ultrafine particle HBeta catalyzer UB a little less than, therefore, its yield of gasoline is higher.
Compound ultrafine particle HZSM-5+HBeta catalyzer UBZ shows both synergistic effects.The sulphur content and the olefin(e) centent of FCC gasoline can be reduced to less than 50 μ g/g with less than 20v% by 300 μ g/g and 46.8v% respectively, and anti-knock index ((R+M)/2) loses less than 1.0 units, the quality of gasoline yield reaches 90wt%.Simultaneously, less catalyzer coke content is indicating that catalyzer has stability preferably.
The above results shows, adopt the ultrafine particle zeolite catalyst of method preparation of the present invention to be applied in FCC gasoline hydrofinishing/aromizing combination process, not only can reduce the content of FCC sulfur in gasoline and alkene, and the loss of anti-knock index ((R+M)/2) is less than 1.0 units.
Claims (12)
1, a kind of ultrafine particle zeolite aromatized catalyst, weight with catalyzer is benchmark, its composition comprises: transition metal oxide and lanthanide rare metal oxide content sum are 1.0wt%～10.0wt%, the ultrafine particle zeolite content is 50.0wt%～90.0wt%, surplus is an inorganic oxide adhesive, and the grain fineness number of ultrafine particle zeolite is 20nm～800nm; The B acid amount of this catalyzer is 0.020mmol/g～0.080mmol/g, and L acid amount is 0.100mmol/g～0.250mmol/g, and total acid content is 0.120mmol/g～0.330mmol/g.
2, according to the described catalyzer of claim 1, it is characterized in that transition metal oxide is one or more in zinc oxide, ferric oxide, manganese oxide, nickel oxide, cobalt oxide, molybdenum oxide and the Tungsten oxide 99.999, the lanthanide rare metal oxide is lanthanum trioxide and/or cerium oxide.
3, according to the described catalyzer of claim 1, it is characterized in that transition metal oxide is zinc oxide, nickel oxide and molybdenum oxide, the lanthanide rare metal oxide is a lanthanum trioxide.
4, according to the described catalyzer of claim 1, the specific surface area that it is characterized in that catalyzer is 300m
2/ g～550m
2/ g, pore volume are 0.15ml/g～0.45ml/g, average pore diameter 1.5nm～3.5nm.
5,, it is characterized in that the ultrafine particle zeolite is HZSM-5 and/or HBeta according to the described catalyzer of claim 1.
6, the described Preparation of catalysts method of claim 1 may further comprise the steps:
A, ultrafine particle zeolite and inorganic oxide adhesive are mixed, through rolling, behind the extruded moulding, drying, roasting, preparing ultrafine particle zeolite Aromatizatian catalytic agent carrier intermediate;
After b, said catalyst carrier intermediate carry out hydrothermal treatment consists, adding equivalent concentration in the ratio of liquid/solid volume than 1.5: 1.0～5.0: 1.0 is the dilute inorganic acid solution of 0.1～2.0N, after rinsing, drying, roasting, prepare ultrafine particle zeolite Aromatizatian catalytic agent carrier;
C, with above-mentioned carrier incipient impregnation in the aqueous solution that contains transition metal and lanthanide rare metal, then, filter, dry, roasting, prepare the ultrafine particle zeolite aromatized catalyst that contains transition metal oxide and lanthanide rare metal oxide.
7, according to the described preparation method of claim 6, it is characterized in that the hydrothermal treatment consists process described in the step b is warming up to 500～600 ℃ under being 1: 1～10: 1 water vapour atmosphere at water/solid volume ratio, and thermostat(t)ed water thermal treatment 3～15 hours under this temperature.
8, according to the described preparation method of claim 6, it is characterized in that the diluted mineral acid described in the step b is hydrochloric acid, nitric acid, phosphoric acid or carbonic acid, its equivalent concentration is 0.2～1.0N, described rinsing, drying and roasting process stir rinsing down in temperature being 20～100 ℃, 100 ℃～140 ℃ dry 8～15 hours down, 400 ℃～500 ℃ following roastings 3～10 hours.
9, the arbitrary described ultrafine particle zeolite aromatized catalyst of claim 1～5 is in the hydrogenating desulfurization of catalytic gasoline of whole fraction and the application in the aromizing combination process process, and its process comprises: first section employing Hydrobon catalyst carries out mild hydrogenation to catalytically cracked gasoline and makes with extra care; Second section is that first section hydrotreated product carries out aromatization on above-mentioned ultrafine particle zeolite aromatized catalyst.
10,, it is characterized in that first section mild hydrogenation refining reaction condition is: reaction pressure 2.5MPa～4.5MPa, 180 ℃～280 ℃ of temperature of reaction, volume space velocity 2.0h according to the described application of claim 9
-1～10.0h
-1With hydrogen to oil volume ratio 200～800: 1.
11, according to the described application of claim 9, it is characterized in that the reaction conditions of described aromatization is: reaction pressure 2.5MPa～4.5MPa, 340 ℃～420 ℃ of temperature of reaction, volume space velocity 0.5h
-1～3.0h
-1, hydrogen to oil volume ratio 200～800: 1.
12,, it is characterized in that Hydrobon catalyst and ultrafine particle zeolite aromatized catalyst series connection filling according to the described application of claim 9.
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